JPH01502200A - Deicing composition containing calcium magnesium acetate double salt and method for producing the same - Google Patents

Abstract

Compositions which comprise a calcium magnesium acetate double salt are useful in deicing compositions. Deicing compositions comprising those compositions and processes for their preparation.

Description

[Detailed description of the invention] calcium magnesium acetate Deicing composition containing double salt and its manufacturing method Background of the invention Removal and/or melting of snow and ice on roads, bridges, sidewalks, etc. is a major task in many areas. be.

Various chemicals are used to aid in the removal and/or melting of snow and ice. usually Road salt has become popular in part due to its melting properties and also to its relatively low price. It is widely used. However, the low price of salt means that it can be used not only for cars but also for roads, caused by its use on bridges, underground cables (e.g. telephone lines or electric wires). offset by damage caused by The corrosive nature of salt affects the steel structures and surrounding structures of pavements and bridges. cause damage. Moreover, accumulation in running water causes problems in plant growth. ground water (accumulation) causes health problems in drinking water due to increased IJum content. Potassium chloride Other salts such as lucium have been used, however, calcium chloride also It also has similar problems, causing the accumulation of chloride ions in the environment, which is undesirable. Not.

Therefore, alternative deicing chemicals that are non-corrosive, environmentally acceptable and economically viable has been widely studied.

Federal Highway Administration is a de-icing chemical product. Regarding BjOrkat6n 1esearch Laboratory (B RL) sponsored extensive research. Report of this research”　Alternat ive Hlghway Deicing Chemical ”1980.3 Monthly recommends calcium magnesium acetate ( CMA) was confirmed. Since the publication of this BRI report, various groups and individuals have Calcium Magnesium Acetate, Calcium Acetate and/or Magnesium Research on the preparation and testing of deicing agents containing umacetate. (e.g. US Patent No. 4,426,308, Series No. 4,444,672, No. 4,511,485 and 4,606.836).

However, producing CMA economically on a commercial scale has been problematic. example For example, Gancy, Alan B''Preparation of Hlg h Quality Calcium Magnesium Acetate U sing a Pilot Plant Process”, Feaera See lHlgway ALministratiOn (January 1986) Do it. Dry large clumps of CMA in the product remove unacceptable levels from this product. This was a problem because it produced temporary dust. For example, June 3, 1985, Ceaarapid for WaH1ghway Re5search Board Continuous proauctlon made by S Inc. Calcium Magnesium Acetate / 5ana Dei See carl'l.

The traditional method is to remove powdered lime dust and recycle materials, bed materials and products in Exhibited unacceptable levels of acid odor and vapor issues.

Conventional calcium magnesium acetate coated sand deicing agent uses cement as binder Wetting agents such as grinding aids were used. Rlppie U.S. Pat. No. 4,588, See No. 512.

Gancy U.S. Pat. No. 4,699,725 describes magnesium calcium acetate. Discloses a sheet composition and a method for producing the same.

No. 003,097 filed January 14, 1987 by the applicant, Al. A deicing composition containing a potash earth or alkali metal carboxylate and a method for producing the same are disclosed. Show. No. 77,148 incorporates the disclosure of U.S. Patent Application No. 003,097. A de-icing composition comprising lucium magnesium acetate double salt is disclosed. This US special No. 77.148 is incorporated herein by reference.

Summary of the invention The present invention provides a calcium magnesium acetate double salt useful as a deicing composition. The object of the present invention is to provide a composition containing the same and a method for producing the deicing composition.

The deicing composition of the present invention contains crystalline calcium acetate, magnesium acetate and and substantially pure CMA double salt substantially free of unreacted magnesium base.

- In embodiments, these compositions include a CMA double salt that is substantially anhydrous. “Substantially "Anhydrous" means containing less than about 5 parts of water [or calcium or magnesium]. Each mole of um is about 0.45-! For example, an acute double salt is CaMg2 ( If it has the approximate empirical formula of C2H302)6, then this double salt is the CMA double salt. Mole win! D will have 1.35-f or less water]. Approximately 2.5 weight (approximately 0.21 moles of water per mole). The applicant's discovery is CM Composition A preferably has 3 to 4 moles of water per mole of magnesium. (Thus, one with a calcium:magnesium ratio of 1:2) The composition will have about 6 to 8 parts water or about 20 to 25 parts water by weight) .

See U.S. Pat. No. 4,694,725 to Gran (7).

The CMA double salt of the present invention has an approximate empirical formula: C5LxMgy(C2H302)2( , y) (where x = 3 to 4 and y = 7 to 6). Therefore, the force ・Lucium:magnesium ratio is from about 4:6 to about 3=7, preferably from about 3=6 It spans a range of about 3 nia.

The compositions of the present invention substantially contain crystalline CA and crystalline mucilage as demonstrated by X-ray diffraction. Contains virtually pure CMA double salt with no oxidation. These compositions are also thermogravimetrically analyzed - gas Measured by chromatography-mass selective detector (“TGA-GC-MSD”) amorphous (as well as crystalline) MA and unreacted magnesium base as determined. Does not include the above. (This technology extracts the gas generated through thermogravimetric analysis and sets it for 20 minutes. - Gas chromatograph using a mass selective detector set to 200 atomic mass units Put it on. See Examples 14 and 15 for further explanation).

CA,) C and one other composition (see Figures 7A, 7B, 7G and 7F) (See Figures 7C, 7D and 7G) ) and from CA 1MA, physical mixtures of CA and kites and other compositions. (Fig. 5A to 5C, Fig. 6B, Fig. 6C, Fig. 1OA to 10D, Fig. 11) (see Figures A to 11D and Figures 12A to 12D) and T()A of the present invention - ()C-MSD spectrum (Fig. 6A, Fig. 8A to 8D, and Fig. 9A to 9D) ) describes herein that the CMA double salts of the present invention are distinctly different from other compositions. CMA double salt is calcium acetate or magnesium acetate or these two. have properties different from any of the two physical mixtures. For example, the CMA double salt of It differs from lucium acetate and/or magnesium acetate in water solubility. Ru. Laboratory studies have shown that this double salt is much less soluble in water than CA or MA. It is shown that Additionally, this CMA double salt can be analyzed by X-ray crystallography (described in Example 16). Steps and 7C.

7D and 7F) and TGA-GC-MSD analysis (as described in Example 15). (see Figures 8A to 8D and Figures 9A to 9D). It appears to have a characteristic crystal structure as clearly shown.

Additionally, these deicing compositions contain calcium acetate and magnetite on a molar basis. Demonstrates improved ice melting behavior over that expected for mixtures of siacetate . This is surprising in view of the aforementioned poor solubility of the CMA* salt in water.

In accordance with a preferred embodiment of the present invention, the cubic foot particle specific gravity of 91.2 or greater is at least 4 Bulk density of 0 pounds and attrition of less than approximately 6 inches (ASTM D 4058- A CMA double salt composition consisting of pellets of substantially equal size having a Served. Other excellent handling properties of these compositions include their extremely uniform particle size distribution. and low dust and acetic acid odor.

Thus, using conventional machinery to apply de-icing chemicals such as road salt, The deicing composition of the present invention can be sprayed. Furthermore, this relatively high bulk density makes it difficult to Unlike compositions containing CMA, these deicing compositions can be applied once to snow or ice. If used, it will be difficult to blow away (”Hlgh 5ierra Is 5ite For Ca1francs C1)/IA Te5ts”, - In the specific example, this The deicing composition of et al. comprises multiple layers of the CMA composition of the present invention on discontinuous substrate particles. . The base particles optionally include a friction aid and/or CMA particles.

The present invention also includes 1) about 40% water by weight, about 4=6 to about 3 nia, preferably Calcium and magnesium having a calcium:magnesium ratio of about 3:6 to about 3 nia Preparing an aqueous mixture of magnesium base (“CM salt II5”); (1)l The mixture of step taJ is mixed with a stoichiometric amount of about 70 to about 110 tons of acetic acid to produce a the mixture comprising at least about 50% water by weight to form a slurry; ( C) If necessary, add additional acetic acid to give stoichiometric amounts for the four bases. and (d) aging the slurry of step (C) to dissolve acetic acid, calcium and allowing substantially complete reaction of the magnesium base; substantially free of acetate, magnesium acetate and unreacted magnesium base. A method for producing a calcium magnesium acetate double salt is provided. optionally, before The method includes drying and pelletizing the slurry of fill step (a). nothing. “Stoichiometric amount” means completely reacted with calcium or magnesium ions. means the number of moles of acetic acid (or acetate) required to 2 moles of acetic acid or acetate for each mole of ion.

In a preferred embodiment of the process of the invention, in step (1)) from a stoichiometric amount of about 70 to About 95%, more preferably about 90%, acetic acid should be added at once and the pH measured after mixing. To measure H, dilute the CMA slurry with 1 part slurry to 2 parts water) and If it is greater than about 8 to 8.5, add more acetic acid to reduce - from about 7 to 8.5. Adjust to about 8.5, preferably about 7.5 to about 8. Optionally, lower after the aging process If too much is obtained (approximately 6/2 or less), reslurry CM in water, A Increase to a better range by adding dust (from the dust collector below). Can be added.

In a preferred embodiment of the method of the invention, a continuous process is used. In this continuous method, vinegar Reaction train with sufficient residence time to allow complete reaction of acid and CM base The slurry is aged by flowing through it. The preferred residence time is about 3 1/2 or is within 4 hours.

Longer residence times can be used if desired.

It has been disclosed that hot slurries have advantageous handling properties. Reaction between tetrabase and acetic acid Since the reaction is exothermic, the heat of the reaction alone will cause temperatures within the range of about 130 to 150°F. The slurry temperature is obtained. However, the temperature of the slurry begins to fall below this range. at least 130 to 150"F, preferably about 170 to about 20" It is beneficial to heat the slurry to 0'F. 200°F' or higher as desired temperature can be used.

The method of the invention involves combining the tetrabase and vinegar in essentially stoichiometric amounts in a reasonably dilute aqueous medium. By simultaneously mixing the acids and then aging the resulting slurry, substantially A complete reaction was obtained and was substantially free of unreacted magnesium base and substantially free of unreacted magnesium base. Data obtained by anhydride and also by X-ray diffraction and TGA-GC-MSD Both calcium acetate and magnesium acetate themselves A substantially CMA double salt composition is obtained. This result is similar to other disclosed methods. amounts of unreacted magnesium base and / or a certain amount of calcium acetate and/or magnesium acetate. It is surprising that a product with (From Figure 6B, Figure 60, IOA (see Figures 10D, 11A to 11D, and 12A to 12D).

As noted above, the CMA double salt produced by the method of the preferred embodiment of the invention is substantially Anhydrous, having on the order of less than about 5 parts by weight, preferably less than 2.5 parts by weight of water. (or about 0.45 mole or less per mole of each of calcium and magnesium, preferably or less than about 0.21 moles of water). This is because the stamen composition is preferably magnesium. having 3 to 4 moles of water per mole of water, thus at least about 6 to 8 moles of water This is in contrast to this teaching.

See, for example, GanCy US Pat. No. 4.699.725.

A slightly alkaline CMA slurry is suitable. about 7 to 8.5 - It is also suitable for slurries with Particularly suitable are those having a - of about 7.5 to about 8. ing. This slurry has beneficial alkalinity-values that reduce damage to pavement surfaces. yields a deicing composition that Additionally, this slurry is produced during the dispensing and drying process by Acetic acid release, which reduces procreation and also has to be regulated for environmental reasons. advantageously reduced.

In one embodiment of the method of the invention, the drying and pelletizing steps are performed on discontinuous substrate particles. In a thin layer - involves dispensing the slurry and drying the substrate particles.

The substrate particles are inert supports, such as friction aids, fertilizers (sidelight, urea, ammonium phosphate, etc.). um, phosphate rock, etc.) or other aggregates; or pre-7 ohm ABC particles. It can contain either. Repeat the dispensing and drying process until the deicing agent reaches the desired particle size. Apply multiple thin layers of ABC until Because it is fluid and can be used with a pump. To this end, the slurry generally contains at least about 50 parts by weight water. About 55? A slurry containing approximately 68% water is suitable. Preferably, the slurry during the process) to a temperature of about 100 to about 250°F, preferably from about 170 to about Heat to a temperature of 200'F. In order to be able to use fluids and pumps, It is necessary to heat the slurry, which has a low moisture content, to a much higher temperature. Distribution and drying process can be performed at substantially the same time.

A variety of materials can be used as the substrate onto which the CMA slurry is dispensed. The preferred substrate is polished Contains chafing agents and pre-7 ohm CMA particles.

Therefore, the above method penetrates ice quickly and has dimensions of ) High enough density to have uniformity, substantially equal size shape, and ease of handling granules of pellet hardness for maximum deicing effectiveness with minimal dust problems. A CMA double salt deicing composition is provided.

The deicing compositions produced by the above method are of substantially equal size and have the desired throughput. It has a particle size within a wide or narrow size range with a large or small average size.

For example, from a small 48 tile mesh (diameter approx. 0-295mm) to approx. ．． Deicing composition with a size range of 571 (5) inches (approximately 9.5++Im diameter) Can prepare things. - In the specific example, this dimension is within the -5 to +28 mesh dimension range. be. This is done in part because it is easy to use with regular machinery for distributing deicing compositions. particle size is suitable.

Product size can be adjusted by selecting the appropriate mesh size product sieve. Ru. For example, using 7 mesh products (fine materials), the specification of 90% + 8 mesh 90 mesh minimum + 9 mesh using near/2 mesh sieve according to specifications matches.

Unless otherwise specified, the following terms have the following meanings:

The term "slurry" may be used even if the solution contains or does not contain insoluble suspended matter. Indicates a solution of a soluble substance above the saturation point of the soluble substance. (For example, U.S. See Patent No. 3,333,297). For example, AKC slurry is AEC solution or This is a solution containing both dissolved ABC and undissolved AEC, as well as unreacted raw materials.

The term "alkaline earth" refers to elements in group 1 [a] of the periodic table, such as lium, calcium, magnesium, strontium, barium, radium, etc. include.

The term "alkali metal" refers to elements in group 1a of the periodic table, such as lithium. Contains umium, sodium, potassium, rubidium, cesium, francium, etc. The term "AE base" refers to an acetate that can react with a carboxylic acid to form a carboxylate salt. Indicates an alkaline earth or alkali metal base or a mixture thereof. Representative AE bases includes oxides, hydroxides, carbonates, etc. of alkaline earth and alkali metal elements. child The AE bases can include one or more of a variety of group elements.

The term ``calcium and magnesium bases'' or ''yy bases refers to the alkali bases mentioned above. The earth or alkali metal moiety contains calcium, magnesium or mixtures thereof. Indicates a superbase.

The term "magnesium base" means that the alkaline earth or alkali metal moiety mentioned above is Indicates a superbase containing gnesium.

The term ``AEC'' refers to an alkyl group in which the carboxylate group has from 1 to 4 carbon atoms. Indicates a potash earth or alkali metal carboxylate or a mixture thereof. terminology AEC is calcium acetate, magnesium acetate and potassium acetate single salts such as calcium and magnesium acetate, as well as mixed salts such as calcium magnesium acetate. physical mixtures or crystallization products of single and/or mixed salts. include.

The term “CA” or “calcium acetate” refers to anhydrous calcium acetate. The term “MA” or “magnesium acetate” refers to both of its hydrates. Both hydrated magnesium acetate and its hydrate are shown.

The term “calcium magnesium acetate” or “CMA” refers to the empirical formula Ca , Mg2(acetate)2(W+2) (where W is the mole of calcium, z is the mole of magnesium). Calcium magnesium acetate composition with and thus have essentially any molar ratio of calcium to magnesium 1 shows a calcium magnesium acetate composition.

The term ``1 calcium magnesium acetate double salt'' or ``CMA double salt'' means Si and magnesium co-crystallize together to form calcium acetate and magnesium. Calcium magnesium acetate salt without physical mixture of acetate and this salt has an empirical formula consistent with that described above for CMA. CMA complex The salt appears to have the following approximate empirical formula: CaXMgy(acetate)2( x + y), where x = 5 to 4 and y = 7 to 6° What is the term °calcium-magnesium ratio” or 1-calcium-to-magnesium ratio? Shows the ratio of moles of calcium to moles of magnesium.

All 6 fractions are expressed as weight percentages unless otherwise specified.

The term "friction aid" refers to an agent that aids and improves friction when applied to slippery surfaces. Denote a substance. The term therefore includes inert supports with good anti-slip properties. Granulated sand, crushed lime, powdered cornstone, cinder, good anti-slip substances, such as other substantially insoluble substances that have inhibitory properties.

The term “mesh” refers to the mesh size measured by the Tyler standard single sieve series. Show the law.

The term "slurry" refers to slurry measured by diluting 1 part slurry to 2 parts water. Indicates - of slurry.

Brief description of the drawing FIG. 1 is a schematic diagram showing the steps of one embodiment of the present invention.

FIG. 2 shows a solder combination distributor-dryer device used in one embodiment of the method of the present invention. FIG. 3 is an elevational view of the iagram characteristics.

3 is a longitudinal section through the drum element of FIG. 2 and its end fittings; FIG.

4 is a cross-sectional view of the drum element of FIG. 2; FIG.

Figure 5A is TGA-()C-MS for crystalline calcium acetate hemihydrate. It is a figure showing a D spectrum.

Figure 5B shows TGA for crystalline magnesium acetate tetrahydrate -()C-M It is a figure showing an SD spectrum.

Figure 5C shows crystalline calcium acetate hemihydrate and crystalline calcium acetate hemihydrate having a 1:1 weight ratio. TGA-GC-MSD for physical mixture of magnesium acetate tetrahydrate It is a figure showing a spectrum.

FIG. 6A shows a cvp double salt sample of the present invention having sample layer B8105-02-6. It is a figure showing a TGA-GC-MSD spectrum.

Figure 6B shows a 1:1 calcium:magnesium ratio sample scrap B8105-40-3. For the 90 MA sample prepared according to U.S. Pat. No. 4,606,836, It is a figure showing a TGA-GC-MSD spectrum.

Figure 6C shows the calcium:magnesium ratio of 6:7 and sample/16B81D5-40. -5 to the 90 MA sample prepared according to U.S. Patent No. 4,606,836. It is a figure which shows the TGA-GC-MSD spectrum for.

Figure 7A shows the X-ray diffraction pattern for crystalline calcium acetate hemihydrate. It is a diagram.

Figure 7B shows the X-ray diffraction pattern for crystalline magnesium acetate tetrahydrate. This is a diagram.

FIG. 7C is for a CMA double salt sample of the present invention having sample layer B8105-02-5. FIG. 2 is a diagram showing an X-ray diffraction pattern.

Figure 7D is for a CMA double salt sample of the present invention having sample layer B8105-02-6. FIG. 2 is a diagram showing an X-ray diffraction pattern.

Figure 7E has a 1:1 calcium:magnesium ratio and sample 4B8105- 02-4 shows the X-ray diffraction pattern for a CMA sample.

Figure 7F has a calcium:magnesium ratio of 3.3:67 and is prepared at low temperature. X-ray diffraction pattern for a sample with sample/16BS669-23-2 FIG.

Figure 7G is without stacked crystalline erosion peak points, and Figures 8A to 8D are as described in Example 10. 'I'GA　-GC for the CMA double salt sample of the present invention prepared by the method described above. - It is a figure which shows an MSD spectrum.

Figures 9A to 9D show CMA double salts of the invention prepared according to the method described in Example 10A. It is a figure showing a TGA-GC-MSD spectrum for a sample.

IOD diagrams from 10A are TGA for commercial CMA samples from Verdugt. -()C-MSD spectrum.

Figures 11A-11D were prepared in accordance with U.S. Pat. No. 4,699,725 at 2:8. TGA-GC-M for CMA samples with a calcium:magnesium ratio of A diagram showing SD is shown below.

Figures 12A to 12D are 1:2 prepared according to U.S. Pat. No. 4,699,725. TC)A　-GC- for a CMA sample with a calcium:magnesium ratio of It is a figure showing MSD.

Detailed description of the invention This CMA slurry is then prepared by preparing a fluid, pumpable CMA slurry. υ produced according to the invention by the method comprising drying and pelletizing the A CMA double salt composition was prepared. Discontinuous substrate particles (which are optionally CMA or abrasive) at least about 130 to about 150' F. , preferably having a temperature of about 170 to 200"F. By drying the lever base particles to produce a granular (or pelletized) deicing composition. Preferably, the CMA slurry is dried and pelletized.

Production of CMA slurry Typically, the base, acetic acid and water are mixed, preferably in a stirred vessel. A CMA slurry is prepared by. Preferably one base and water are mixed first and the producing a flowable aqueous CM base mixture that typically contains at least about 40% water by weight. : Next, add acetic acid. The CM base is reacted with a sufficient stoichiometric amount of acetic acid to CM that provides complete reaction of alpha bases and minimal acid vapor loss and also has low corrosivity A CMA slurry having a composition A is produced. Preferably acetic acid versus CM base The ratio of Minimize volatilization of unreacted acid during the process. Therefore, add enough acetic acid to react with the α base. correspondingly from about 7 to about 8.5, more preferably from about 7.5 to 8.0 p)l (water 2 When diluted with 1 part slurry to 1 part slurry), it produces a CMA slurry with a substantially acid odor. There isn't. Optionally, re-slurry collected (during the distribution and drying process) by a dust collection device. Chemical dust may be added to the slurry.

This addition can be achieved without increasing insoluble matter, which is normally seen at β values of about 8.5 or higher. The rally can be increased to 8.5 or more. The slurry should be about 9 to 10 - (9 parts water to 9 parts water) When one part of the product is diluted with respect to one part of the product), one part of the product is obtained.

A slurry with a low β value (approximately 5 to 6) will prevent oversized products during the distribution and drying process. The production increases and results in high acetic acid emissions which are unacceptable from an environmental point of view. This slurry It produces unacceptable corrosive products that cause pavement discoloration when used for deicing. cause

Pumping fluids that do not solidify by adding sufficient water, either alone or as part of an acetic acid solution. Produces a usable slurry.

A slurry without sufficient water will solidify suddenly, especially when heated. Slurry or about 50 If it contains water below the weight ratio (on the order of about 30 moles of water per mole of CMA) Excessive thickening of the slurry occurs at about 170°F'. Uses low slurry moisture As this occurs, the resulting slurry must be heated to a higher temperature. subordinate Thus, a slurry having at least about 50 parts water is suitable.

CMA slurries having about 55 to about 68 inches of water are particularly suitable. big amount You can use a CMA slurry with a water content of Slurry with high water content must be removed and therefore increases drying costs It is less economical and profitable.

Additionally, it is better to use a lower slurry moisture content before distributing and drying the resulting slurry. It requires heating to a very high temperature.

Suitable CM bases include calcium, magnesium oxides, hydroxides, carbonates, etc. including mixtures of these in various molar ratios.

Preferred alpha bases are dolomite lime, hydrated dolomite lime, preferably sg hydrated dolomite lime. Contains limestone and magnesium oxide.

Suitable alpha bases include impurities such as iron and aluminum which form insoluble acetate salts. It is a lowly thing.

Preferred forms of acetic acid include dilute solutions of acetic acid (as low as about 10%) and concentrated acetic acid, such as glacial acetic acid. and an acetic acid solution with an intermediate concentration. The acetic acid used here is a chemical method. It can be produced by other methods such as fermentation of cellulosic materials by yeast or microorganisms. Ru. Acetic acid produced by other methods, such as microbial fermentation, can be produced by conventional methods used in chemical engineering. The more concentrated acetic acid that is produced is also advantageous from a cost standpoint; l) Increased yield due to the need to further evaporate water to obtain a dry product. This would overcome the economic disadvantage of drying costs.

Suitable acetic acids include glacial acetic acid.

This CMA slurry is aged to allow complete reaction of acetic acid and CM base. with acetic acid When using reactive CM bases with relatively short reaction times, the slurry may be aged. It is preferable to This is due to the fact that some containers reach the age of drying and pelleting. This can be done by flowing through a reactor train. Approximately 3.5 to 4 A reactor train with a residence time of give more than enough time.

Longer stays, on the order of about 10 to about 13 hours, or longer, as desired. Reactor trains with residence times can be used.

Production of de-icing composition from CMA slurry Preferably, the fluid, pumpable CMA slurry is about 100 to about 250' P, preferably at a temperature of about 150°F, more preferably from about 170 to about 200’F Heat to. Surprisingly, relatively high temperatures, preferably from about 170 to about 20 Heating the CMA slurry to 0°FI increases efficiency and therefore yield in the subsequent distribution process. found that the rate was improved. Additionally, high slurry temperatures are required when preparing CMA. It has been discovered that retaining as a CMA double salt results in the production of a much higher proportion of CMA. Ta. Further, when the slurry is not heated to a sufficiently high temperature, e.g. When heated below, most of the slurry forms a thin layer on the substrate particles during the distribution process. Rather, it becomes dust. Remove this dust from the baghouse or wet scrubber. must be collected in a highly efficient dust collector such as recirculate to.

Thus, the overall amount of water that has to be removed during the drying process increases, and this Increase costs.

Furthermore, another beneficial effect of operating at high slurry temperatures is that the hardness of the CMA coating decreases at low speeds. It was found that there is a 50 factor increase for high slurry temperature operation compared to slurry temperature operation. Ta. The increase in hardness of the pond coating is due to dust and fines during product transportation and storage. It provided a product that could better resist deterioration to form.

As mentioned above, the CMA slurry remains fluid and pumpable and solidifies. The CMA slurry must contain sufficient water so that it does not. This slurry is one Generally contains at least about 50% water. In particular, having about 55 to about 68 water Suitable for slurry. Low slurry moisture content also results in higher dust and fines during the distribution process. Causes the formation of things. Required high slurry moisture content reduced with increased drying costs Generates manufacturing efficiency.

In one embodiment of the method of the invention, a CMA slurry is distributed onto discrete substrate particles. A thin layer of CMAO is produced on the substrate particles. From about 1001”’gs preferably about 0 Atomizing air from about 20 psig can be used. Surprisingly, on the base particles Not using extra atomizing air when dispensing slurry results in increased product It has also been discovered that the amount of slurry that becomes dust and fines is reduced. preferably wherein said thin layer of CMA substantially surrounds said substrate particles and is a substantially continuous layer. form. The layered base material particles are then dried. Desired particle size for the deicing composition Dispense while adding an additional thin layer of C1,U with each dispensing and drying cycle until and recirculating the layered substrate particles through a drying process to deposit a large number of C on the substrate particles. produces an MA layer.

Suitable substrate particles are inert supports, such as friction aids, fertilizers (e.g. urea, phosphoric acids). ammonium, phosphate rock or other age resort, or preformed 0MA particles It is. Particularly preferred substrate particles are sand, especially sand of -10 to +20 mesh size; and preformed 0MA particles. Breformed particles are produced by this method. Grind a deicing composition with a layer of CMA such as the one prepared and place it on an inert support. (in some cases) by separating the CMA material from the desired dimensions A designated portion of the product is recycled to obtain oversized particles, which are then ground and pre-processed. By providing a source of formed 0MA particles, 7 ohmed CMA is provided. Ru.

Distribution and drying steps can optionally be carried out simultaneously, e.g. in the presence of heated gas. Dispensing a thin layer of CMA slurry onto the substrate particles, or sequentially dispensing and drying It can be done separately.

In one preferred embodiment, the dispensing and drying steps are performed substantially simultaneously. In this specific example, heating This step is carried out on a densely falling curtain of substrate particles in the presence of a gas (e.g. air). Distribute the lari. This process occurs virtually simultaneously when the slurry is distributed in a thin layer onto the substrate particles. The heated gas contacts the substrate particles. droplets of slurry are dispensed onto the substrate particles; The water then splashes off leaving a dry coating of CMA on the substrate particles. Base material Flow rate and temperature of heated gas to cause water to splatter from the thin layer of CMA slurry on the particles. Adjust. Optionally, small substrate particles are recycled through the combined distribution and drying process. C to the extent necessary to ring to produce the desired particle size in a product of substantially equal size. Provides an additional layer of MA. If the breformed material constitutes the base material, the dimensions of the product grinding or crushing large particles to obtain a continuous source of broken particles; can use small particles without grinding.

The layered substrate particles are sieved to remove fines and recycled for CMA application. Receive additional layer: feed large material to a suitable crusher.

Using this method, alumina with various proportions of individual alkaline earths and alkali metals Ice agents can be prepared by adjusting the types and amounts of alkaline earths and alkali metals. yielding the desired content of various alkaline earths and alkali metals. Therefore, here we use Adjust the alkaline earth base to about 4:6 to about 627, preferably about 3:6 or A deicing composition comprising a CMA double salt having a calcium to magnesium ratio of about 3 nia will occur.

FIG. 1 is a specific example of the method of the present invention.

In FIG. Water is supplied through the inlet 10. At the same time, the CM base (“AE”) is passed through line 14. base 41'''') and if one or more CM bases are used, line 16 CM base waste 2 ("AE base/S62") is supplied into the tank 12 through the tank 12.

If additional CM bases are used, add them to the tank through additional supply lines. It can be supplied to 12. This mixture is passed through line 18 to reactor 22 with optional agitation. The acetic acid (“carvone powder”) is supplied to reactor 22 through line 20. , which reacts with the CM base to produce a CMA slurry. This CMA slurry is The surge tank 26 is filled through the line 24. Collected from the dust collector 66 The collected dust is supplied to the surge tank 26 along with additional water if indicated.

Heating device 28 heats the slurry in surge tank 26 . A preferred heating device 28 is including steam jackets, steam coils or other heating devices. Sprayed slurry or contact Impinging on a dense curtain of substrate particles cascading from the lid 36 in the container 34 The surge is passed through the line 30 through the spray nozzle 32 located in the contactor 34 as shown in FIG. Pump the heated slurry from tank 26. The substrate particles are connected through line 38. Inlet or layered substrate particles enter contactor 34 through recirculation line 40 . This layered crystal The particles are dried in a dryer 42. Gas flow through line 44 to heating device 46 (where it is heated by natural gas or other suitable heating device) and then This heated gas is then drawn through line 48 into dryer 42 . - Preferred equipment In this example, the contactor and dryer are installed so that the substrate particles are dried immediately after coating. Combine (see Figures 2 to 4). In another embodiment, the contactor and dryer are separated. It is. The layered substrate exits the dryer through line 50 and enters separator device 52 .

Separator device 52 is removed and contactor 34 line 5 is removed for additional coating. Take out the fines returned through 4-40. Large materials are powdered through line 56. Enter the crusher 58 (preferred crushers include a 1-mer mill or roll crusher), then and returns to contactor 34 through lines 60-40. Pull the product through line 62. out and then sent for transportation and storage. (If the base particles include CMA particles, any Optionally, a designated portion of the product may be recycled to the contactor 34 to obtain a larger material that can be used next time. to produce CMA substrate particles). Alternatively, a rotating drum cooler or fluidized The product can be cooled in a bed cooler or other suitable cooling device.

Continuously feeding substrate particles to contactor 34 through line 38 (or recirculation 40) Ru. The amount of material in the contactor 34 and the internal structure of the contactor 34 can be adjusted to control the return of emitted particles. Provides the least amount of scratches and the most uniform level of coating on each particle.

Air and dust are removed from dryer 42 through line 64. Dust collection equipment At stage 66, the dust is collected. Suitable dust collection devices 66 include, for example, a baghouse, including a wet flapper or other conventional dust removal system. Through line 6B to exhaust air to the atmosphere (outside). Dust collection Reclaimed dust collected by each device is returned to the surge tank 26 through line 70.

(Alternatively, if each dust collection device includes a wet flapper, the CMA da The mixture of gas and water is returned to the mixing tank 12 through a conduit).

In the method of manufacturing the deicing composition of the present invention, a pre-7 ohm powder containing a friction aid Alternatively, either small CMA particles or an inert support can be used as the substrate particles.

Figures 2 through 4 depict combination dispensing-drying suitable for use with preferred embodiments of the present invention. Show the device. This device is a modification of Tytus et al. U.S. Pat. No. 3,333,297. c is well described and is incorporated herein by reference.

In summary, the combined dispensing-drying apparatus shown in Figures 2 to 4 is mounted for rotation. The drum 102 includes a hollow elongated drum 102. The substrate is passed through conduit 104 to drum 102. to go into. Vanes 106 are routed in conduit 104 toward vanes 108 that line drum 102. Help the transferred feed substrate. Vane 108t - shown in cross section in FIG. Conduit 11 0 to transfer the CMA slurry to the spray nozzle 112. Approximately 0 to approximately 100 p”i Atomizing air pressures preferably from about 0 to about 20 psig can be used. spray nozzle It is particularly preferred that no extra atomizing air be used in the system. Use extra atomizing air It has been found that this reduces the amount of slurry that becomes dust and fines. spray Atomizing air at approximately 20 to 80 psig will cause the coated substrate product to stick to the lifter. I believe this is necessary to prevent the slurry from adhering to the substrate particles. This is surprising, since it has been Conduit 113 directs hot gas to the drum. provide As the drum 102 rotates, the vanes 108 cover the drum vertically and lengthwise. This curtain acts as a shower of substrate particles across the drum. and move. Sprayed through a nozzle onto multiple moving curtains of slurry or substrate particles A thin layer is distributed over the particles and this is passed through a drum to the hot drying gas. It is thoroughly dried. The substrate particles traverse the drum 102 at the exit end of the drum 102. This spraying and drying action is repeated as the dam 114 is reached. Manifold 116 accepts both hot gas and substrate particles. The substrate particles enter the receiving device 118 and From there, it is sieved and, if indicated, recirculated into drum 102. be done.

Another embodiment of the invention uses separate dispensing and drying equipment. separation distribution system Suitable equipment for this purpose are drum granulators, pan granulators, pug mills and other conventional granulators and Including pelletizer. Preferred separation drying equipment includes rotating drums and fluidized bed dryers and and other conventional equipment for drying pelletized or granulated materials. The slurry is on top This apparatus is used with sufficient substrate particles to produce a rotating bed of substrate particles to be disposed. Ru. Sufficient force is applied to build up a layer on the substrate particles to give a product of the desired size. The device is adjusted to produce a recirculation ratio.

Continuous production of CMA double salt In one preferred embodiment of the invention, the unreacted magnesium base is first and substantially An anhydrous, substantially pure double salt is produced by a continuous process.

Water, calcium and magnesium bases (e.g. calcium oxide, acid ibimagnesium) CM and dolomitic lime) to form an aqueous CM base mixture.

Add sufficient water, at least about 40 parts by weight, to form a flowable mixture.

This CM base mixture and a stoichiometric amount of about 70 to about 110 units of acetic acid are simultaneously added together. In addition, approximately 1.8 moles of siacetic acid (stoichiometric amount) per mole of calcium and magnesium A steady state of 90% is produced. Adding too little acid or adding acid too slowly If added, by-products will form and precipitate (e.g. calcium as a white precipitate) magnesium acetate and magnesium acetate as an amorphous precipitate).

Optionally, maintain a slurry of about 7 to 8.5, preferably about 7.5 to 8. Add additional acetic acid. Monitor the slurry: Slurry with 1 part slurry to 2 parts water. After diluting the slurry, - of the slurry thus diluted is measured.

ions of acetic acid and then this slurry for a sufficient period of time to allow substantially complete reaction. to mature. in a series such that the total residence time is sufficient for a substantially complete reaction. This aging can be accomplished by flowing the slurry through a container.

A residence time of the order of about 3.5 to 4 hours has been found to be sufficient: Long periods of time (on the order of about 10 to about 15 hours) can be used. Acetic acid and 0M base The heat of reaction produces a slurry temperature of over 150°F' and about 170 to 200°F. F is within the preferred range; however, during the ripening process the temperature must be kept within the preferred range and It is desirable to heat the slurry to maintain its fluidity.

After ripening, a temperature of at least 150F, preferably from about 170 to about 200"F' Heat this slurry (if necessary). Next, apply this slurry to the substrate as described above. Dispense onto particles and dry.

Calcium Magnesium Acetate Double Salt Calcium to Magnesium Ratio of Approximately 1:2 Compositions of the present invention comprising substantially pure crystalline 01.4A double salt having CA, MA and different from physical mixtures of CA and MA, but also made from other methods. and several properties that differ from other CMA compositions that are not substantially pure CMA double salts. shows.

The substantially pure C1-mu double salt of the present invention has crystalline CA as evidenced by X-ray diffraction. and substantially free of crystalline MA. This X-ray diffraction technique is described in Example 16. C The substantial absence of A is approximately 5.2 and 7.420, the strongest component of crystalline CA. manifested in the virtual absence of

The virtual absence of crystalline MA is at its strongest at approximately 12.5 to 13 degrees 2θ. Manifested by the virtual absence of peaks. From 2θ8.75 to 10. A characteristically very strong cleavage within a range of 5° is observed for crystalline double salts: These peak positions are centered at approximately 9.1 and 9.820.

The amount of crystalline CA and MA impurities can be specified from the X-ray diffraction pattern. That's how it is Then, the shear strength for the CMA peak located at F19.1 and 9.8° is combined. plus the peak intensities for the CA peaks located at approximately 5.2 and 7.4 Centered at approximately 12.7° 2θ <2 times the peak intensity for MA. fruit The quality pure crystalline CMA double salt is preferably about 8% or less, based on the total of the two CMAs. or have a percentage of impurity vinyl equal to or less than F151.

Substantially pure crystalline CMA double salts of the present invention can also be obtained by T()A-oc-MSD. substantially free of amorphous (and crystalline) and unreacted magnesium. Contains no bases. This technology extracts the base released from thermogravimetric analysis (TGA). and a mass selective detector (TGA-G) set at 15 to 200 atomic mass units. These are subjected to gas chromatography using C-MSD).

As discussed in Examples 14 and 15, T by mass relative to CO□ and/or acetone Virtual absence of kites from 29 to 65 minutes when monitoring GA-GC-MSD , i.e., as evidenced by the virtual absence of peaks at about 290 to 350°C. same Sometimes unreacted magnesium base, Mg(OHz) or magnesium oxide hydrate When either is present, a peak occurs at 300°C. Compared to CMA, Unreacted magnesium base in amounts greater than about 1% by weight can be detected by this technique. Not yet Reactive bases may be found in some of the products produced by direct reaction methods disclosed by others. but not found in the products produced using the slurry process of the present invention.

TGA - ()C - From MSD - and the amount of magnesium base impurity can be calculated . The resulting acetone spectrum is monitored in order to calculate the amount of bulk impurity. Effortless Area under the peak at approximately 29 to 39 minutes (approximately 290 to 350°C) corresponding to purity Area under all acetone peaks from 20 to 45 minutes (200 to 450 °C) Compare to. Thus, MA a7tone release can be measured as a percentage of total acetone release. Wear. Calculated in this manner, a substantially pure crystalline interstitial double salt contains 5% of this MA impurity. It does not have the above. To calculate the amount of magnesium base impurity, the resulting water space was Monitor vectors. The area under the peak that appears at about 600℃ is magnesium hydroxide. This corresponds to water from aluminum or magnesium dispersion impurities. Substantially pure crystalline double salt is about 3% by weight or less, preferably about 1% by weight or less of basic impurity of magnesium. Having this percentage of things.

As noted above, the substantially pure CMA double salt of the present invention is substantially free of all of the following: : Crystalline CA: Crystalline and amorphous MA: and unreacted magnesium base.

More particularly, the substantially pure tetradouble salt meets the following criteria: t This is a crystalline CA and a crystalline criminal as evidenced by the X-ray diffraction pattern. i.e. for the sum of two strong single peaks (as discussed above). The sum of the impurity peaks for CA and islands is less than or equal to about 8, preferably less than or equal to about 5. Chill below.

2. TGA-C) C-MSD measurement shows that it is amorphous (and crystalline) MAt-substantially free and free of magnesium base, i.e. no muacetone release The output should be less than 5% of the total acetone released: and the magnesium base impurity (approximately 30% (as measured by water release at 0°C) is less than about 3% by weight of the CMA sample, preferably 1% by weight. It is as follows.

Substantially pure CMA double salt compositions include crystalline CA, crystalline decomposition, and crystalline CA and kite. Physical mixtures (Chapter 5A.

5B and 50 respectively) or manufactured by other methods. When compared to the composition (see Figures 6B and 60), T()A -GC-MSD min. When performing the analysis (see Figure 6A) it shows a striking pattern.

T()A-()C-MSD shown in Figures 5A to 5C and 6A to 6C The analysis was conducted with acetone and carbon dioxide (acetate) with respect to time at a constant heating rate of 107 min. The relative ion abundance (abundance θ) of the main decomposition product) is plotted.

Reduce the carbon dioxide abundance by a factor of 3 to match the acetone abundance scale. The fine structure of GO-MSD chromatodarum is shown. This method is further illustrated in Example 14. and 15.

FIG. 5A shows TGA-GC-MSD analysis of crystalline CA hemihydrate. base Essentially, CA decomposes when heated to produce acetone and calcium carbonate: calcium carbonate. Lucium further decomposes to produce carbon dioxide. Very small amount of carbon dioxide plotted Note that it is detected during the given time frame. Most of the carbon dioxide is in the 5th It is released at a higher temperature than that represented in Figure A (approximately 600 to 800°C).

FIG. 5B shows T()A-GC-MSD for crystalline particles. Most of the members are from CA. However, magnesium carbonate decomposes at a much lower temperature and therefore cannot be produced. Similar Co2 is detected during the plotted time frame.

Figure 5C shows TGA-GC-MAD for a physical mixture of CA and bird. 1 A mixture was prepared by co-milling CA and gourd with a :1 weight ratio.

FIG. 6A shows TGA--MSD analysis for CMA double salt according to the present invention.

Comparison with the analyzes shown in Sections 5A, 5B, and 5C shows that this sample contained the least amount of CA and kite. Indicates that it contains.

The proposed decomposition mechanism or reaction formula is as follows: CaxMgy(C2H302 )2 (x+y) →XCaCO3+ 7Mg0 +2(x+y)CH3COC H3+ 7CO2 (300-500°po) xcacO3-+) xcao + xcO2(500-800'(Y) Assuming the formula, 'I'GA data The x/y ratio was calculated to be 0.55, which corresponds to the elemental analysis of the sample of 0.52. The results match well. Therefore, the TGA-()C-MSD of this sample is approximately 1 to approximately Substantially pure calcium magnesium with a calcium to magnesium molar ratio of 2 Indicates that it is um acetate double salt.

Figure 6B shows the method disclosed in U.S. Pat. No. 4,606,836 (the "direct reaction" method). ) with a calcium to magnesium acetate ratio of approximately 1:1 Shows TGA-GC-MSD analysis of CMA samples. Ratio to Figures 5A and 6A From the comparison, it was found that this sample reached the peak temperature monitored by the molecular weight of acetone at about 40 and 42 minutes. Contains a significant amount of residual CA, as clearly shown.

Figure 6C shows 3-nia calcium produced by the same direct reaction method as the sample in Figure 6B. TGA-'()C-MSD analysis of CMA sample with um-to-magnesium ratio show. This sample is also not of the invention. 5A% 5B and 6A From the comparison, it can be seen that the sample amount contains a significant amount of both residual CA and MA.

When subjected to analysis by powder X11A @ folding, the crystalline CMA double salt of the present invention is crystalline A CMA composition that is CA and crystalline MA and a substantially impure CMA double salt (No. 7A to 70) has a characteristic pattern.

From the x gauze fold patterns shown in Figures 7A to 7F, crystalline CA, crystalline MU and CM It can be seen that all A double salts exhibit characteristic X-ray diffraction patterns. Further explanation of the method Described in Example 16. Table X summarizes the zero position for CMA double salts of the present invention. Ru.

Figure 7A shows a conclusion with the two strongest - one at 20 of about 5.2 and about 7.4. 1 shows an X-ray diffraction pattern for crystalline CA hemihydrate.

Figure 7B shows the X-ray diffraction pattern for the crystalline tetrahydrate. This is 2012 ．． 5 to 13 show the strongest peaks. Amorphous MA is centered around 1020 It shows a very wide diffraction mark.

Figure 7C shows X-ray diffraction for a double salt according to the invention. In this figure, for crystallinity Sharp vertical lines for corresponding peak positions are stacked. Double salt is 208.75' shows a characteristic very strong double-single characteristic within the range of 10.5 to 10.5. These -one The ri is centered at approximately 91 and 9.8. Strongest crystalline MA Vp-ri does not exist First, this sample appears to contain virtually no residual crystalline material. two 20 range of the strongest CA peaks (5, 2 and 7.4) with very low intensities The peak indicates that this sample contains very small amounts of residual crystalline CA, and therefore It appears to consist of substantially pure CA double salt.

No. 7D is also an X-ray analysis of the CMA double salt according to the present invention in which crystalline peak points are stacked. Indicates the time. This sample has a strength within the range of 208.75 to 10.5, which is characteristic of Otori double salt. It shows double-one. A very small amount matching the 2θ range for the strongest crystalline wear. The absence of the strongest crystalline MA peak coupled with the presence of always lower intensity peaks is This sample has virtually no residual crystalline MA and only very small amounts of crystalline CA. This indicates that the salt contains a substantially pure double salt.

Figure 7E shows a 1:1 ratio of calcium to magnesium produced by the slurry method of Example 7. Figure 3 shows the X-ray diffraction pattern of a CMA sample not of the present invention with the ratio. this sample The diffraction pattern of shows the double peak characteristics of CMA double salt, but also shows the double peak characteristics of crystalline CA. The moderate intensity peak corresponding to the 2θ value of the strongest peak and the maximum of crystalline MA Also shows low intensity peaks corresponding to the 20 range of strong peaks. Therefore, that Examination of the line diffraction pattern shows that while this sample contains a single double salt, it also contains a medium salt. It contains about 100% of crystalline Yu and some crystalline MA, so it is substantially pure. It seems that it is not a double salt.

Figure 7F has a calcium to magnesium ratio of 3 to 7 but at low temperature according to Example 11. Figure 3 shows the X-ray diffraction pattern of a CMA sample produced that is not of the invention. this test The diffraction pattern of the material shows a double peak characteristic of Ike double salt, but it also shows a double peak of crystalline CA. Shows moderate intensity peaks corresponding to the 2θ dry range of the two most intense peaks. Therefore , this sample contains a moderate amount of crystalline CA and is substantially pure CMA double salt. I don't think so.

Figure 7G shows the present invention without the stacked lines corresponding to the peak positions of crystalline CA. The X-ray diffraction pattern of a sudden sample is shown. This pattern is used in this example for crystalline CA and MA. Indicates the absence of Table XI summarizes the positions and intensities of these peaks. Ru.

Additionally, the CMA slurry is heated to a relatively high temperature during the process of producing the deicing composition. It has a higher proportion of crystalline CE'A double salt compared to CA and/or MA. It has been discovered that deicing compositions can be produced that 7th C, 7D.

See 7F and 7th part diagram.

Figure 8 shows the TGA-GC-MSD diagram for the CMA sample prepared according to Example 10. TO-A for the C1a sample prepared according to Example 10A. -GC-MSD spectrum is shown. Figure 10 was manufactured by Veraugt. The TGA-GC-MSD spectrum for a commercially available CMA sample is shown. Figure 11 Gan C7, U.S. Pat. No. 4,699,725, approximately 2 to 8 calcium to A CMA sample prepared by the method of Example (1) containing gnesium is shown. Figure 12 is G ancy U.S. Pat. No. 4,699,725, approximately 1:2 calcium to magnesium. Example 3 shows a CMA sample prepared by the method of Example 2B, which contains Uno and Ratio.

Part A of each of these figures shows the total ion kalanthra. Part B of the diagram is time, therefore is shown as a function of temperature and the CO2 generated at 1. Part C of the diagram is time, therefore temperature shows the water generated as a function of . Part D of the diagram is as a function of time and therefore temperature. Shows the acetone generated.

As can be seen by comparing Figures 8 to 11, the present invention is as shown in Figures 8D and 9D. The sample prepared by the method of Akira was produced in less than 65 minutes (approximately 350 minutes) and showed an acetone spectra. It contains virtually no peaks in the torsion and therefore contains virtually no magnesium acetate. stomach. Commercially available samples and disclosures to others as shown in Sections 10D, 11D and 12D The samples prepared using the method described all exhibit significant MA jerk.

Table 16 shows the X-ray diffraction and TGA-()C-MS for some samples of CMA. D data is shown. This data shows the X-ray for CMA double salt at 9.1 and 9.82θ. the peak intensity for crystalline CA impurities (5, 2 and the peak located at 7.420).

This table also shows the amount of water in the sample, as measured by TGAK, and TGA. - As measured by the ratio of acetate/peak produced in GC-MSD, The amount of This MA seventone release is calculated as the c fraction of the total acetone release. It will be done. Both of these samples have unreacted magnesium base, so this design Data-10-11-87 is a sample of substantially pure crystalline aCλ double salt. other X-ray diffraction data showed that the sample contained a significant amount of crystalline CA or T'GA-GC-MSD. MA i with acetone data generated from: These samples are clearly substantially pure. This shows that it is not a crystalline double salt.

The following non-limiting examples are representative of deicing compositions made according to the method of the present invention. Practically the first Using an equipment with a combination dispensing and drying bag M as shown in Figs. Examples 1 to 7 and Example 10 were prepared.

Unless otherwise specified, after diluting the slurry with 1 part slurry to 2 parts water, then The OpH of the diluted slurry was measured.

Example 1 Patch production of calcium magnesium acetate on sand The entire calcium magnesium acetate (CMA) slurry is prepared by the following process. Manufactured using the batch method. Water 72 was charged to a stirred ventilated reaction tank. S type Hydrated amite lime 150 bond was added gradually. A homogeneous slurry of lime in water occured. Pour technical grade glacial acetic acid into the tank at a rate of approximately 1.0 fnd/min. The pump was sent. As this acid is added, the heat of reaction between the acid and lime increases the temperature of the mixture. caused an increase. When all 186.5 bonds of acid were added, the slurry became too thick. vinegar Rari temperature was 130°. Add 8 ml of water to completely dilute the slurry. acid combination Acid addition was resumed until a total of 239 pounds had been added. Slurry pJ (was initially 8.2 The temperature rose to 8.8 after being left overnight. The slurry moisture was 68 degrees.

This water content is a little lower than what was calculated for the mass balance, and a small amount of evaporation occurs. It was shown that Subsequent batches of slurry were made similarly, but became viscous during the soup stock reaction stage. A large amount of water was added at the beginning to avoid oxidation.

CM to a granular deicing composition containing CMA'i coated on sand by the method described below. Completely convert A slurry. 6 ft diameter by 12 ft long pilot plant All rotating drums were used. This drum has an internal lifter, an internal dam and an external solids recycler. Equipped with a circulation system. Also) baghouse on en, inlet air heater and outlet air An air system consisting of a dust collector was also included.

, 2. Charge sand plasting grade sand 500 bond into this rotating drum. Ta. The system was preheated to approximately 150°C. The sand particles fall in the rotating drum. CMA slurry at a temperature of approximately 112'F into a spray nozzle positioned to spray onto the pipe. Re'fr: Pumped. The inlet air was heated to 575'F. Slurry spray speed was adjusted to 0.3 gpm as shown on a magnetic flowmeter. 50 psig spray air Spraying System nozzle, body number 601 for slurry tanking at atmospheric pressure 50 and cap number 120 was recirculated back to the inlet of the ram. This spray slurry coated the sand particles and dried at the same time. As you continue this process, the CMA A uniform off-white coating formed on the sand particles. Signs of particle agglomeration There was no problem. Inspection of baghouses reveals large amounts of very fine, lightweight dust. It was indicated that it would be collected by the hopper. CMA coating on the sand when spraying continues. increased steadily over time. As the spraying continued, 16, 27, 36 Samples consisting of particles with 1 and 56 CM coatings were drawn over time. did.

Calculate the spray yield (spray yield by coating on sand rather than dust) The weight percent of CMA) was shown to be only 42. (This is not commercially possible. A high degree of dust recirculation will always be necessary and production rates will be significantly reduced and (which meant that the drying costs would increase considerably due to the low spray yield).

The composite particles consisted of individual sand particles substantially uniformly coated with an outer shell of Ck4A. . Measuring the crushing strength of CMA shells shows that it decreases as the CMA percentage increases. It turns out. With the highest percentage of Cum and the softest shells, the shells can be normalized without appreciable damage. Hard enough to withstand storage and handling. Crush strength of outer shell of 56% CMA pellet The strength was 2.8 pounds measured in force r-ge.

The solution of the product is 27% mixed with 3 parts of water, 1 part for 1 part of CMA product. It was 0.2. Final product containing 56% CMA I tested at 60.8 lbs. / cubic foot.

The ice melt tendency of the 36% CMA product was tested at 27°F'.

The pellets quickly adhered to ice. Visible liquid forms in 5 minutes and is visible. The melting continued for 90 minutes.

A liquid outflow of 129 mm was observed after 90 minutes of melting time for 100 mm of 3610MA pellets. Against F It was then measured.

The basic process outlined in Example 1 was as follows.

Most of the CMA in the slurry spray becomes dust rather than a coating on the particles. It was clear that the spray coating efficiency (substrate particle A test was conducted to determine the percentage of CMA in the coated I'Jli. . Combined with reading the slurry tank level to measure the amount of CMA input Slurry tank for water percentage, measure initial weight of sand placed in rotating drum and then the percentage of CMA present as a coating on the sand particles. This was done by analyzing CMA coated sand. Spray yield is mainly due to It was discovered that it depends on the temperature. Slurry moisture, excessive unreacted lime, particle temperature Other variables such as grain size and 15FW atomization have a much smaller effect on coating effectiveness. Have a friend. of runs on CMA slurry produced by the reaction of dolomite lime and acetic acid. The results are shown in Table 1. This data indicates that the spray coating yield is greater than 1551 for slurry. It shows that it is much higher when heated to the top.

In practice, the formed dust is collected and placed in a slurry tank along with additional water. must be recirculated to

A friend who makes all of the slurry from re-slurry dust and tests it. for this case The coating yield was also highly dependent on slurry temperature, as shown in Table 1.

The data in Table n shows that the jet coating yield is higher with reheated slurry, but However, the slurry made by reacting lime and acid cannot be re-slurried. Indicates that it is not high against dust. Dust formation due to small changes in slurry temperature The ability to adjust should have been rubbish. The appearance of the slurry does not change significantly upon heating. This dramatic effect on coating yield can be seen from solubility data or slurry granulation. would not be expected from conventional experience with

Another beneficial effect of operating at high slurry temperatures is that high slurry temperatures The hardness of the CMA coating increased by 50 degrees against temperature manipulation. It's been found. The increased hardness of the CMA coating reduces the risk of damage during product transportation and storage. A product was provided that was well resistant to deterioration to form dust and fines.

Spray coat with slurry method to produce calcium magnesium acetate coated sand 135-150 155-165 Moisture, temperature 62-70 62-709L fog coating yield, % 52-61 7 8-　90枦■Table Reslurry bughouse dust? Use 0. <Using the slurry method of covering sand with A Effect of slurry temperature on yield slurry conditions: Temperature, 'F 79 170 Moisture 1 Chi 65 6 Low 67 Spray coating yield, 062 CMA coating by continuous process using the same pelletizing equipment as described in Example 1. produced sand.

Sand was continuously fed into the inlet end of the rotating drum. The front part of the drum in Sura IJ’ Sprayed onto solids that moved in minutes.

The conditions used in the initial run result in a high proportion of solids being emitted from the exit end of the drum. , these solids were continuously returned to the inlet end of the drum. Frequently remove some of the solids at the outlet. A constant amount of solids was kept in the drum. Coated sand particles in conditions of high solids recirculation rate It can be easily seen that the coating has a wide range of coating thicknesses. some of the new sand supply Moving the drum quickly did not receive much CMA coating. sand supply The higher the coating level, the better the different parts of the drum will have long residence times in the drum. received the letter. This product consists of a less heavily coated sand and a more heavily coated sand. It was made of a mixture of particles and had the appearance of salt and pepper.

The rotating drum has an intermediate tube consisting of a tubular member with a depth of approximately 15 mm the diameter of the drum. was established. This so that most of it is available on the floor of the drum spray impingement stroke. The dam ensures the build-up of particulate matter in the drum. This dam has a bed t at the end of the run. A date was set up so that we could meet each other.

After the above test, it was found that the dates in the dam did not seal properly, which is due to the low rise and high stiffness. It was found to cause a systemic recirculation rate. This dam should be sealed and linked to a continuous sand supply. A new run was performed with subsequent product withdrawals. Can be operated without recirculation It turned out to be. This produces a product with a uniform level of CMA coating. I discovered that this occurs. Operating conditions t for this run are shown in Table 2.

After 3.5 hours of operation, the removed product was sieved into fractions of different sizes and separated. Each fraction i was analyzed for CMA coating percentage. The results are shown in Table ■ .

This result indicates that the majority of the products are within the size range of -6 to +20 mm. and this coating level has been shown to be reasonably uniform within this size range. vinegar.

Continuous reactor operation was demonstrated in another test run. No unusual operational problems occurred. operation Conditions t - summarized in Table V.

As the data in Table V shows, due to the reaction of lime and excess, There was an increase in p) (.

Feeding speed: rot, 2 sand, India/time 105 Habutsu slurry, gpm 0.33 Slurry conditions: Moisture, 壬　68 Temperature, 'F170 Drum operating conditions: Outlet air temperature, 'F 164-175 Spray atomized air, ps i g 50 Product withdrawal rate, bond/hour 140 Product analysis: 0 (starting bed) 26 4-5 36.5 Tyler sieve number Weight % 4 CMA+6 1.9 63-0 -6+10 8.8 47.5 -10 + 12 21.2 35.3 - 12 + 14 30.2 26.9 -14 + 20 34.0 18.7 - 20 + 28 3.0 24.5 -28 0.8 42.2 feeding speed Mixing tank: Water, bond/hour 146 Lime, bond/hour 37.5 Reactor: Acetic acid, bond/hour 60.0 Operating conditions Reactor: pH (undiluted) 6.6-7.4 Temperature, 'F' 155 Moisture, Chi 60 Residence time, minutes 7.8 Surzo tank: P) ((undiluted) 8.6 Example 4 During the production of the C1/A coated sand composition by the steps described in the example above, It has been discovered that the product concentration is significantly higher than that of the slurry in which the product is made. Very little Tests were conducted to see what the product pH was for operations with slurries that were acidic. I did it. This slightly acidic slurry is expected. pH of 6.3 to 6.8 It was found that a slurry with a pH of 12 to 9.8 to 9.8 io, o produced a product with a pHt of I'll watch it. Results for operations with slurries having pH=i of 6.3 and 6.8. It is shown in Table ■.

The outlet from the rotating drum was tested at the baghouse outlet for acetic acid to ensure that the acid volatilized. We measured whether there was.

The results showed 30 to 80 ppm acetic acid by volume, depending on the slurry. 6. At slurry levels of 6 or higher, the outlet has a concentration of 50 ppm. Ta.

At a slurry level of 6.3, the concentration of sulfuric acid at the outlet was 8 ppm. Thus , the apparent excess acid in the slurry volatilized; Even when there was no acid loss, there was some acid loss. However, these acid losses were measured The acetic acid flow rate in A was measured at the outlet and the outlet at 30-s o ppm. Extremely small based on concentration. This loss is the production v C1l/, 1 of the total acetic acid in A. It was calculated to be less than or equal to This acid loss is not a significant mortality factor.

Despite this, this increase during the coating operation is fully compensated by the aforementioned acid vapor loss. This is therefore surprising. (a small amount of saline magnesium acetate) It is possible that tate is formed by this acid loss; (I don't think this is a sufficient explanation for the increase.) However, this increase... It is always beneficial and desirable because minimal insoluble, unreacted lime is neutral or (by neutralization) to an acidic final slurry, but at the same time R, W, 5chenk ”　Ice　-Meltlng Characterstlcs　Of　C alcium Magnesium Acetate, Final Report ts, Executive Summary”1985+February research PH′l high enough to avoid concrete peeling that occurs below P) 48. &: Due to the fact that a product with - is obtained.

46 5:5 Sand 6.3 9.8 48 4:6 Sand 6.7 10.0 45 3 near sand 6.5 10.0 40 5 = 5 c 6.8 9.8 47 4:6 CMA 6.5 9.944 3 Near C1/, A 6.4 9 ．． 8 1 part chisurari and 2 parts water Calcium that does not contain high levels of magnesium using high calcium content lime The process outlined in Example 1 was followed for the umacetate gold mains. The process described in Example 1 I made a slurry. Charge 7 of liters of water to the reaction tank and Genstar Lime Co., San Mateo, Calif. Fornia, 85% Ca(OH)2 min) 150 lbs. Glacial acetic acid 20 0 bond gradually added to friend. Towards the end of the acid addition, the slurry became very viscous. water 2 added Ron to dilute the slurry.

Convert this slurry to calcium acetate coated sand following the steps outlined in Example 1. Ta. Test run conditions and results are summarized in Table II. No operational problems occurred. run Medium dust 44 bond was recirculated into the slurry. The results shown in Table 1 show that sand is treated with acetate. Calcium whose coating method is similar to the results for calcium magnesium acetate shown to produce results for muacetate. Slurry temperature is low, 82 to 9 4" F, therefore the spray coating yield was low, 34" F. This discovery results in lower yields at slurry temperatures than calcium magnesium acetate. The results were consistent with the results for

Table 11 Operating conditions Slurry moisture, CH 66.8 Slurry temperature, 82 to 94 Artificial air temperature,. F+550 to 600 air temperature. P175 to 210 Slurry feed rate, gpm O-3 to 0.4 Results: Calcium at the end of the run Acetate q621.4chi Referring to Table 6 of the total baghouse dust and feed, the same as mentioned in Example 1 Run numbers similar to 46.48 and 45. Producing CMA-coated sand using the process However, using a mixture of dolomitic lime and magnesium oxide It produced a very high magnesium content. The magnesium oxide used was grade 20. Type 325 (National Magnesia corporation.

MOBB Landlng+California). Furthermore, add a little slurry A complete lime reaction was obtained by making it acidic. Heating the slurry before spraying increases spray yield It was a big deal.

As shown in Table 1, the - of the final product is from 9.8 to 10.0, and the The residual base level in the product was very low. This product is fcCMA coated. It has high crushing strength and high product bulk density against crushing.

Run numbers 35°40.47 and 44 in Table 11 were performed using a process similar to Example 1. However, essentially no sand was used. Solid C)/, A grains in a rotating drum The first material used to establish the child bed was 56% aMA-coated gold dust. Then, sieve all the crushed material with a 24-mesh sieve to separate the CMA particles from the sand. obtained by separating n. -24 mesh CMA particles as starting bed All used. Commercial operations involve crushing large products or portions of products of fixed size. and provide small particles that can be recycled and coated with a slurry feed. from the drum Small particles can also be removed from the discharged material by sieving and then pulverized. recycled materials.

As the data in Table 11 shows, the bulk density of the product is 38. 4 to 44 pounds, lower than that for sand-coated products, but good handling High enough as a characteristic. Runs 35 and 45 had 24 meth yielding small size products. A vacuum product sieve was used.

For runs 47 and 44, 10 mesh product sieves yielding much larger products. It was used. Further, by using a product sieve with larger pores, Even products of large dimensions can be produced. Crushing strength of straight CMA pellets with higher slurry temperature operation (run 40) and with lower calcium versus mag improved along with the nesium ratio (runs 47 and 44). The pellet wear test is against wear. It shows very good resistance to the product, which means that dust formation is not a problem during product handling. and showed.

Example 8 Coat the simultaneous reaction using a cement mixer. Calcium magnesium acetate coated sand by direct reaction method using kisser Manufactured.

Put sand (42 sandblasting grade) 25 bond into the cement mixer. Ta. The internal lifter of the mixer produced a dense curtain of sand. Water 1 bond kl! J It was sprayed onto the sand using a jig nozzle. Powdered lime, S-type hydrated dolomite lime 1.79 lbs. was added to the wet sand. Ice vinegar using an atomizing nozzle! 2.4 7 lbs. was sprayed onto the sand-lime mixture. After this acid addition is complete, approximately 30 minutes Continued mixing.

The compositions prepared according to the above process are disclosed as sample numbers 1 and 2 in Table X. .

Example 9 Calcium Magnesium Acetate Using Rotary Drum Pelletizer-Dryer Manufacture of coated sand by the following process: Rotating drum pelletizer - direct using dryer Calcium magnesium acetate coated sand was produced by a reaction method.

Rotating drum pelletizer so that the sand is recirculated from the drum outlet to the drum inlet The dryer was charged with 9500 pounds of sand (A62 sandblasting grade).

The front part of the drum continuously sprays water onto the sand before it reaches the lifter. Ta. Lime (S-type hydrated dolomite) is continuously supplied to this front part. ). After the wet sand and dry lime mixture is sent to one part of the lifter, Add acetic acid (up to 67 lbs.) onto the mixture using an air atomizer at 1 liter. g<fog.

A flowable mass of discrete particles with a slight sour odor was obtained.

The composition prepared according to the above process is disclosed in Table X as Sample A3.

Calcium magnesium acetate (CWA) is produced on a commercial scale by the ill method described below. ) All deicing agents were manufactured. Approximately 1440 lbs/hour of S-type hydrated dolomite lime and oxidized macerate A covered and agitated mixing tank (reactor) with approximately 750 lb/hr of gnesium Continuously water (at a rate sufficient to maintain approximately 62% by weight CMA slaly IJ t) at the outlet of the Added target.

solidify into the throat of the eductor using water as the educting medium. Magnesium oxide is produced by drawing magnesium oxide into the body as a slurry with water. Added gnesium. The resulting mixture is passed through a series of four additional mixing vessels by gravity. It flowed due to The entire trough overflows into the next one.

Overflow the fifth mixing tank to the reactor at a rate of approximately 9.6 gallons/minute Add glacial acetic acid at , with thorough high shear mixing, resulting in an exit pH' of approximately 5.6. High etiquette Vent the reactor through a Nerya wet scrubber to reduce acetic acid emissions to the atmosphere . Water is continuously blown out from this flapper and used as supply water to the first mixing tank. I used it. As the slurry overflows into the second reactor, a small amount of excess acetic acid is removed. The slurry pH was maintained at about 6.0 in the slurry tank.

The overall average formulation for the CMA slurry was as follows: Acetic acid 0.8 lb/dry CMA lb S base lime 0.23 bond/dry CMA 0.11 lb. of magnesium oxide/1 lb. of dry CMA resulting in a slurry of approx. Maintaining a temperature of 186'F, the rgrLH nozzle was injected into the rotating drum. It was sprayed onto a falling bed of CMA pellets in front. This drum has an internal lifter, An internal dam and an external solids recirculation system were installed.

Also includes a Mayu fan, inlet air heater and baghouse dust collector on the outlet air. Ru. Temperature of approximately 700”F and approximately 29,000 standard cubic feet 7 minutes (SCF’M Air is introduced at a flow rate of ). Air leaves the drum at about 151'F and enters the atmosphere. Before entering, I entered Bug I Us to remove dust. recovered from this back house Approximately 1,500 pounds of dust per hour is recirculated to the slurry tank and approximately 68 pounds per hour are recycled to the slurry tank. Additional water was added to maintain a moist slurry.

The system separates the CMA pellets formed or enlarged in the drum by sieving. It was similar. Pellets that do not pass through the 34-inch sieve) are crushed and sent to the front of the drum. Recirculated. Pellets passing through the 30 mesh sieve were also recycled. t Approximately 5% of the pellets within the product range of inches + 30 meshes are drawn as product. It is then discharged to storage and recirculated to the front of the remaining 951Th drum.

The product produced from this run has a calcium/magnesium molar ratio of approximately 0.45. has a pH of about 9.5, i.e., 3.1 to 6.9 [about 1 to 2.21], It contained approximately 1.86 weight parts of water-insoluble material.

- Calcium magnesium acetate) () on a commercial scale by the following continuous process: CMA) A deicing agent was manufactured.

Approximately 2120 bonds/hour S-type hydrated dolomite lime and approximately 990 pounds/hour oxidized macerate Along with the gnesium, about 42% of CvA sla IJ leaves the reactor train. Water was added continuously to the stirred mixing vessel at a rate sufficient to maintain t-water. generate The mixture flows by gravity through the additional mixing vessel, passing through the trough from one to the next. It overflowed to that of.

When it overflows into the second mixing vessel, it is poured into the reactor with thorough stirring for about 11 minutes. Glacial acetic acid was added at a rate of 3 gallons/minute, resulting in approximately 9 exits. Slurry or second reaction When overflowing into the vessel, keep approximately 7.5 slurry in the slurry tank. Addition of a small stream of acetic acid? Added L. This reactor is a high energy wet scraper. venting through the air to reduce acetic acid emissions to the atmosphere. Used as feed water to the first mixing container. water from the flapper was used continuously.

The overall recipe for the CMA slurry was as follows: Acetic acid 0.79 lb/dry CMA lb S-type lime 0.26 lb/dry CM A pound magnesium oxide 0.12 bond/dry CMA bond result slurry Maintain temperature at approximately 190'''F (88°C), pump into spray nozzle and cycle. CMA pellets fall onto the floor in front of the rolling drum! It was foggy. To this ram Nine equipped with internal lifter, internal dam and external solids recirculation system. Mako fan, enter The air system also includes an inlet air heater and a baghouse dust collector on the outlet air. included. A temperature of approximately 800’F (427°C) and approximately 32,000 standard cubic feet Air was introduced at a flow rate of 500 kg/min (SCFM). Air is approximately 200″F (93°C) It exits the drum and enters a baghouse for dust removal before entering the atmosphere. Ba Approximately 500 bonds/hour of dust collected from the greenhouse is recycled to the slurry tank. Then add additional water to maintain approximately 58% water content by weight + 7 = 2.

After leaving the drum, any CMA formed or used in the drum The sieved portions were classified using a system. 6 ~ Metsuyu sieve Yoshi big Pele The cut was crushed and recirculated to the front of the drum. Smaller than 8 mesh sieve Pellets were also recirculated. Approximately 5 pellets from the drum to 16 mesh + If the product is within the range of 8 meshes, it is withdrawn as a product and transferred to storage, and the remaining The 95 liters were recirculated to the front of the drum.

The product produced from this run contains approximately 0.46 (approximately 1:2.2) calcium/ water having a magnesium molar ratio, a pHt of about 9.5, and a weight range of about 2.1. Contains insoluble material.

Lime (S-type dolomite), magnesium oxide and water are combined in a beaker and poured. A friend who made Rari. Rice vinegar was added to this slurry. Stir the resulting slurry for 14 hours. 1 of the slurry to give a final slurry temperature of approximately 130 to 140”F. 11) (measured: approximately 5.0 to 7.0 with additional acetic acid as needed) - was given within the range. This slurry was completely filtered through filter paper to remove insoluble matter. about The filtrate was dried overnight in a vacuum oven at 95 to 100°C to yield a low@CMA sample.

The samples were prepared according to the process described above and are disclosed in Table 1.

B5669-23-1 Lime 10.0 5: 5Mg0 Q.4 Wednesday 108.04 Acetic acid 18.56 B5669-23-2 Lime 5.00 3.3: 6.7 (shown in Figure 7) MgO1,90 The X-ray pattern in Figure 7F shows an incomplete reaction to the CMA double salt at this low temperature. did.

Deicing using Chatilon DPP-1 cage (durometer) The crushing strength of the CMA layer of the product was measured.

One rotation around r-ji is equal to the force of 10 bonds f and fc (the division is 0.1 bonds In f increments:)fc). Particles to be treated are forced into the plunger/disk of the I placed it in the lab shack directly below the assembly. Particles that should be treated are properly retained. Raise the lab shack using the height adjustment screw until the end. The force r-ji was set to 0. C Pressure was applied to the particles until the MA layer fractured; at this point the force was not applied.

The results are shown in Table X.

Example 13 Measurement of abrasion resistance Measuring abrasion resistance of CMA deicing compositions using ASTM D 4058-81k My friend.

Results for moderate CMA compositions reported in percentage loss with respect to abrasion are shown in Section X. Display in table.

TGA-GC-MSD emission analysis using direct reaction and slurry method ( Nine CMAs were prepared and compared in both Examples 1 to 9). This technique has been used over time The gas released from the standard thermogravimetric analyzer (T()A) is removed as it is manufactured. The gas was then subjected to capillary gas chromatography (0-C). Mass selective detection The gas at the end of the GC column was analyzed using an instrument (MSD). some presses The total ion calanthine was monitored over time at the cut mass. Approximately 5 representative analyzes I did it in 0 minutes.

The T()A used was Dupont 951 TGA, this is no rths. It was set to be controlled by a tar microcomputer. G C-MSD Hewlett Packard with 5970 quadruple MSD t- It was 5890 AGC.

This aC used a 15 or 50 m 5c-32 capillary column (cross-linked chill silicone, film thickness 0.63 microns, inner diameter 0.30 microns). T The GA outlet was connected to a GC injector. GC input system t-io.

:1 ssolit ratio was set. Add all transfer lines between TGA and GC injector. Wrapped with heat tape.

The G C-MSD continuously monitored TGA release.

Monitor gas emissions at mass 18 (water) to detect unreacted magnesium base. did. Magnet oxide at a temperature of about 300°C in TGA or after about 14 to 16 minutes. I was able to infer the reaction of magnesium hydroxide (or water-containing magnesium oxide) to sium. . The lower limit of detection of unreacted magnesium base by the method described above was approximately 1. .

Samples of CMA prepared by the direct reaction method (Examples 8 and 9) contained unreacted magnesium salts. As a basis (CMA) approximately 5 points were shown.

Samples of CMA prepared by the slurry process method (Examples 1 to 7) were essentially detectable. CA, MA and C by TGA-GC-MSD analysis showing no magnesium base Analysis of MA TGA-C) CA and MA standards and CMA samples prepared by both the direct reaction method and the slurry method were compared. This technology Emissions from a standard thermogravimetric analyzer (TGA) as manufactured over time I took out the gas and applied this gas to the low-resolution Squamography (()C). . Gas was recorded at the end of the GC column using a mass selective detector (MSD). . At a preset mass, all ions can be monitored over an hour.

The TGA-()C-MSD apparatus used is described in Example 14.

Unless otherwise specified, the heating rate was 10°C/min and the helium carrier was fully used. A TGA-GC-MSD analysis of the lever was performed. Helium flow rate t-801-1- / minute. Plot the GC-MSD chromatogram as a function of time. Ta. The TGA starting temperature was kept at 25 °C and the molecular weight of acetone, carbon dioxide and water was Relative ion abundance was monitored at and plotted over time.

Additionally, a spectrum plot showing total ion (TIC) vs. time is performed. Ta. For some plots, the two plots are aligned so that they are superimposed on the same figure. carbon dioxide abundance by a factor of 2.5 to 6 to match the setone abundance scale. The amount of dust has been reduced.

CA hemihydrate and M A tetrahydrate target fish k J, T, purchased from Baker. . A CA-MA mixture was prepared by mixing CA and MA in a 1:1 ratio. . A process similar to that described in Example 1 to 10A produces other C'MA preparations. did. The samples used for TGA-OC-MSD analysis are listed in Table X.

Monitor the gas emissions with the corresponding masses of acetone and carbon dioxide and compare them with time. and plotted.

T()A -GC-MSD clock shown in Figures 5A to 5C and Figures 6A to 6C The chromatogram plots the masses corresponding to acetone and carbon dioxide as a function of time. Plot the emissions.

Figures 8A to 8D, Figures 9A to 9D, Figures 1OA to 10D, Figures 11A to 1 TGA-()C-MSD chromatography shown in Figure 1D and Figures 12A to 12D grams is the mass of water, acetone, and carbon dioxide as a function of time. Plot the release as well as total ion content.

8A to 8D CMA double salt according to Example 10 3.3:6.79A to 9D CM A double salt according to Example 10A 3.1:6.9 crystalline calcium acetate hemihydrate , crystalline magnesium acetate hemihydrate, crystalline magnesium acetate tetrahydrate X-ray diffraction was performed on CMA and various CMA samples.

X-ray diffraction of crystalline CA - Part 7A, 7C, 7D.

7E and 7F diagrams to help locate any crystalline CA impurities. I got it. The X-ray diffraction patterns of the CMA double salts are summarized in Table X. 2θ can be Position: d-spacing and relative intensity are shown.

This analysis was performed using a Siemens D 500 diffractometer equipped with a steel tube. (The 2θ values shown in Figures 7A to 7F are for CuKa radiation. ). Siemens DIFFRAC11 software parameter for peak positioning I used all the cages.

The samples used for the X-ray diffraction studies are shown in Table 1.

Figures 7A to 7F show the X-ray diffraction patterns for the samples shown in Table 1.

Table 1 70 B8105-02-5 According to Example 7 3 near 7 o B8105-02- 6 According to Example 10 3.5:6.57 EB8105-02-4 According to Example 7 1:17 F B5669-23-3 According to Example 11 3.3: 6.77 G CMA double salt according to Example 10 3:7 Table x1 X-ray powder diffraction 20 degree interval d, A relative intensity (″) for crystalline CMA double salt 9-8 9-Om C&-13-96,4vvw 18-5-Mg 4.8 vvw i9.8 4.5 vyw 20.9 4.3 vyw 21.7 4,1 vyw 22.4 4. OvvW 23.6 5.8 vvW 23.8 3.7 vvW 24.1 3.7 vvv 25.2 6.6 vvw 25.7 3.5 vvvr Ca-26-13,4vyw Ca-26,93-3vvw C'a-27,6-Mg 3-2 vvw28.1 3.2 vvv 28.9 5.1 vvw 50-6-Mg 2.9 vvw Ca-31,52-8vytv Ca　-Ca(C'2H30z)z・3'5Hzo　, Le, which overlaps with the peak of $ et al. It overlaps with the peak from Mg-α-Mg(C2H:5o2)2.4H20.

(a) vs=100-80; 5=80-60; m=6O-40; W=4 0-20; YW=20-10; V”VW=1O-0(1) Significant Containing a large amount of MA and a small amount of unidentified phase@ (2) Contains a significant amount of crystalline CA.

(3) Contains crystalline 6-MgCC2H502h.4H20.

(4) From Xd peak strength (5) Area under the emitted acetone peak by TGA-GC-MSD Living lessons FIG.

FIG, J FIG., J.B.

FIG., J.C.

FIG, J FIG. J.B.

FIG, -7Q FIG.-? G.

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Claims (46)

[Claims] 1. Crystalline calcium acetate, magnesium acetate and unreacted magnesium Substantially pure calcium magnesium acetate double salt containing virtually no bases A composition comprising. 2. Up to about 8% by weight of crystalline calcium acetate, up to about 8% by weight of magnesia Claim 1 containing umacetate and less than about 3% by weight of unreacted base. composition. 3. Up to about 5% by weight of crystalline calcium acetate, up to about 5% by weight of magnesia magnesium acetate and less than about 1% by weight of unreacted magnesium base. Compositions according to scope 2. 4. A composition according to claim 1 which is substantially anhydrous. 5. A composition according to claim 4 containing up to about 5% water by weight. 6. Up to about 8% by weight of crystalline calcium acetate, up to about 8% by weight of magnesia magnesium acetate and less than about 3% by weight of unreacted magnesium base. Composition according to Scope No. 5. 7. A composition according to claim 4 containing up to about 2.5% water by weight. 8. Up to about 5% by weight of crystalline calcium acetate, up to about 5% by weight of magnesia magnesium acetate and less than about 1% by weight of unreacted magnesium base. Compositions according to scope item 7. 9. TGA-GC-M, which is the same in terms of actual wages as Figures 6A, 8A to 8D or 9A to 9D SD spectrum and an X-ray diffraction pattern substantially identical to Figure 7C, 7D or 7G. A composition according to claim 1. 10. Claims having a calcium:magnesium ratio of about 4:6 to about 3:7. Composition according to paragraph 1. 11. Claims having a calcium:magnesium ratio of about 3:6 to about 3:7. Composition according to paragraph 10. 12. 12. A composition according to claim 11 containing up to about 5% water by weight. 13. TGA-GC-MSD substantially identical to Figures 8A to 8D or 9A to 9D and Claim No. 7 showing an X-ray diffraction pattern practically identical to No. 7C, 7D or 7G. Composition according to item 12. 14. Trial ceremony: CaxMgy(C2H3O2)2(x+y), where x is 3 to 4 and y is from 7 to 6). 15. 15. A composition according to claim 14 containing up to about 5% water by weight. 16. Up to about 8% by weight of crystalline calcium acetate, up to about 8% by weight of magnetism Claims containing siacetate and less than about 3% by weight of unreacted magnesium base A composition according to range item 15. 17. TGA-GC-M substantially identical to No. 6A, 8A to 8D or 9A to 9D It shows an X-ray diffraction pattern that is virtually identical to the SD spectrum and Figures 7C, 7D, or 7F. A composition according to claim 16. 18. 17. A composition according to claim 16 containing up to about 2.5% water by weight. 19. Up to about 5% by weight of crystalline calcium acetate, up to about 5% by weight of magnetism Claims containing siacetate and less than about 1% by weight of unreacted magnesium base A composition according to range item 18. 20. TGA-GC-substantially identical to Figures 6A, 8A to 8D or 9A to 9D X-ray diffraction pattern substantially identical to the MSD spectrum and Figures 7C, 7D or 7G A composition according to claim 19 exhibiting the following. 21. comprising multiple layers of the composition according to claim 14 on discontinuous substrate particles. Deicing composition. 22. 22. A deicing composition according to claim 21, wherein said base particles include a friction aid. 23. The base particles may include particles of calcium magnesium acetate double salt. A deicing composition according to claim 21. 24. Bulk density of at least about 40 pounds per cubic foot, greater than about 1.2 A composition according to claim 14 having a particle specific gravity and an abrasion of about 3% or less. Deicing composition. 25. A bulk density of at least about 40 pounds per cubic foot, greater than about 1.2 A composition according to claim 14 having a particle specific gravity and an abrasion of about 3% or less. Pelleted de-icing composition. 26. Crystalline calcium acetate, magnesium acetate and unreacted magnesium A method for producing calcium magnesium acetate double salt that does not substantially contain sia bases. There, (a) about 46 to about 3:7 calcium containing at least about 40% water by weight; (b) preparing an aqueous mixture of CM bases having a magnesium:magnesium ratio; from about 70 to the stoichiometric amount of acetic acid required to convert the CM base of about 110% of the mixture of step (a) so that the resulting mixture has at least about 50% producing a CMA slurry containing % by weight of water; (c) Optionally, the total amount of acetic acid approximately converts said CM base into said double salt. Add enough acetic acid to the slurry to be the stoichiometric amount of acetic acid needed for to add; and (d) Aging the CM slurry to achieve substantially complete reaction of acetic acid and CM base. thing, The above manufacturing method including. 27. (e) drying the slurry of step (d) and pelletizing the dry free stream; 27. The method according to claim 26, further comprising producing a dynamic product. 28. said drying and pelletizing discontinuous substrate particles of step (e); distributing the slurry of step (d) into the upper thin layer and drying the substrate particles; 28. A method according to claim 27, comprising: 29. In step (e), the slurry of step (d) becomes discontinuous due to the presence of the heated gas. Claims in which the falling substrate particles are distributed in thin layers on such a curtain to produce stratified particles. The method according to paragraph 28. 30. (f) repeating step (e) to form layered particles having multiple layers on the particles; 30. The method according to claim 29, further comprising: generating. 31. step (d) further comprising mixing the mixture of step (a) and said amount of acetic acid; A method according to claim 26 comprising: 32. Step (c) includes measuring the pH of the slurry of step (d), and optionally and adding sufficient acetic acid to produce a pH of about 7 to about 8.5. The method according to Section 31 of the Scope. 33. Claim 2, wherein step (d) is performed at a temperature of at least about 150°F. Method according to Section 6. 34. Claim 1, wherein step (d) is performed at a temperature of about 170 to about 200°F. Method according to Section 26. 35. Claim 34, wherein the CMA slurry contains about 55 to about 68% water by weight. How to read. 36. Step (b) further comprises admixing a stoichiometric amount of about 90% by weight acetic acid. A method according to claim 34. 37. Step (d) comprises aging the slurry for at least about 3.5 hours. A method according to claim 36. 38. Crystalline calcium acetate, magnesium acetate and unreacted magnesium Calcium Magnesium Acid is substantially free of sialic bases and is virtually anhydrous. In the method for producing acetate double salt; (a) containing at least about 40% water and about 4:6 to about 3:7 calcium; (b) preparing an aqueous mixture of CM bases having a magnesium:magnesium ratio; about 90% of the stoichiometric amount of acetic acid needed to convert the CM base into the double salt described above. simultaneously blending the mixture of step (a); the resulting mixture is at least about 50% by weight; % of water to produce a CMA slurry; (c) adding additional acetic acid, if necessary, to produce a pH of about 7 to about 8.5; ; (d) Aging the CMA slurry to achieve substantially complete reaction of acetic acid and CM base. and (e) drying and pelletizing the slurry of step (d). producing a free-flowing product. 39. Claim 3, wherein step (d) is conducted at a humidity of at least about 150°F. Method according to Section 8. 40. Claim 1, wherein step (d) is performed at a temperature of about 170 to about 200°F. Method according to Section 38. 41. on said dried and un-pelletized substrate particles of step (e); distributing the slurry of step (d) in a thin layer with A method according to claim 39 comprising: 42. Claim 1, wherein said dispensing of step (e) is carried out without extra atomizing air. Method according to Section 41. 43. Crystalline calcium acetate, magnesium acetate and unreacted magnesium Virtually free of sialic bases, empirical formula: CaxMgy(C2H3O2)2(x+y), where x is from 3 to 4 and In the method for producing a calcium magnesium double salt having y of 7 to 6) (a) of a CM base having a calcium:magnesium ratio of about 4:6 to about 3:7; preparing an aqueous flowable mixture; (b) about 70% of the stoichiometric amount required to convert said CM base to said double salt; to about 110% acetic acid and the mixture of step (a) to form a CMA slurry. and that this slurry contains sufficient water to be fluid and pumpable. ; (c) If necessary, the total amount of acetic acid added approximately converts the above CM salt to the above double salt. Add enough vinegar to the slurry to be the stoichiometric amount of acetic acid needed to make adding acid; and (d) Aging the CMA slurry to achieve substantially complete reaction of acetic acid and CM base. That, The above manufacturing method including. 44. (e) drying and pelletizing the slurry of step (d) to be substantially anhydrous; According to claim 43, further comprising: producing a dry, free-flowing product. How to do it. 45. Crystalline calcium acetate, magnesium acetate and unreacted magnesium A method for producing calcium magnesium acetate double salt that does not substantially contain sia bases. It is; (a) containing at least about 40% water and about 4:6 to about 3:7 calcium; (b) preparing an aqueous mixture of CM bases having a magnesium:magnesium ratio; from 70 to about 110 stoichiometric amounts necessary to convert the CM base of % of acetic acid and the mixture of step (a) and, if necessary, all of the acetic acid. the amount is approximately the stoichiometric amount required to convert said CM base to said double salt. Adding sufficient additional acetic acid to the slurry to ensure virtually complete reaction. The above-mentioned manufacturing method includes the step of causing a reaction. 46. (a) drying and pelletizing the slurry of step (b) to be substantially anhydrous; According to claim 45, further comprising: producing a dry, free-flowing product. How to do it.